Creation of High‐Speed Carrier Migration Channel through Sulfur‐Modulated ZnSn(OH)6 Electric Fields for Deep Oxidation of C─H Bonds

Abstract The key challenge in the deep mineralization of toluene (C 7 H 8 ) into carbon dioxide (CO 2 ) lies in controlling the efficient selective oxidation of the intermediates. Here, dual‐site photocatalyst (ZHS‐3S) with S 2− doping and oxygen vacancies (OVs) is formed by the in situ introduction of sulfur ions (S 2− ) with relatively low electronegativity to promote the dissociation of strongly electronegative oxygen atoms at tin sites. ZHS‐3S demonstrates impressive performance: 91.95% C 7 H 8 removal rate, complete mineralization, and stability over 600 min. Comprehensive materials characterization and theoretical calculations led to several critical insights: i) the precise coordination of dual sites has created high‐speed charge carrier migration channels centered around OVs, achieving an electron transfer efficiency of up to 93.95%; ii) the optimization of the local electric field establishes an efficient dynamic equilibrium for the adsorption and desorption of C 7 H 8 , ensuring its initial efficacy in catalytic reactions while mitigating aggregation phenomena and the associated risk of poisoning; iii) breaking through the thermodynamic limitation of C 7 H 8 photooxidation, effectively diminishing the Gibbs free energy required for the formation of readily ring‐opening intermediates (benzaldehyde→benzoic acid). These findings offer a novel perspective on incorporating non‐metallic elements with low electronegativities, aiming at the precise design of highly efficient catalytic materials.